Composition Comprising Hueing Agent

ABSTRACT

This invention relates to a laundry care composition comprising a laundry care ingredient and a polymeric thiophene hueing agent.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to and is a divisional of U.S. patentapplication Ser. No. 17/156,771, entitled “Composition Comprising HueingAgent” which was filed on Jan. 25, 2021, which claims priority to U.S.Provisional Patent Application No. 62/983,872, entitled “CompositionComprising Hueing Agent,” which was filed on Mar. 2, 2020, both of whichare entirely incorporated by reference herein.

TECHNICAL FIELD

This invention relates to a laundry care composition comprising alaundry care ingredient and a polymeric thiophene hueing agent.

BACKGROUND

As consumers move toward lower temperature and shorter washing cyclesfor laundry to conserve energy, the cleaning efficiency of laundry carecompositions may not be as effective as at higher temperatures andlonger wash times. Therefore, the use of hueing agents in laundry carecompositions provides a technology that offers a whitening benefit todingy textile articles (e.g. clothing and other garments), making themappear brighter and whiter, even at low wash temperatures and shortcycle times. The use of harsh bleaching chemicals is also not desired asthey can shorten the life cycle of the textile articles and beenvironmentally unfriendly. Furthermore, in some instances, consumersprefer a more reddish-violet shade hue on clothes when masking theyellowing of fabrics which cannot be obtained with bleach formulations.As a result, there is a continued need to improve the whitening effectof textile articles treated with laundry care compositions that containhueing agents. The present invention provides a laundry care compositioncomprising a polymeric thiophene hueing agent which has beendemonstrated to whiten textile articles, such as cellulose-containingfabrics. Incorporating this hueing agent in a laundry care compositionprovides one possible and successful delivery mechanism for depositiononto a textile substrate. Each time the textile substrate is washed, thehueing agent is deposited on the textile substrate. Thus, the textilesubstrate is continually whitened, and the life cycle of the article maybe extended.

BRIEF SUMMARY

In one aspect, the invention relates to an aqueous laundry carecomposition comprising a laundry care ingredient and from 0.0001 wt % to1.0 wt % of a polymeric thiophene hueing agent having the structure ofFormula I:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers; wherein each R₁ isindependently selected from H, C₁₋₄ alkyl, alkoxy alkyl, halogens, aryl,substituted alkyl or substituted aryl, —COR₂, —CH₂COH, —COOR₂, —COOH,—SO₃H, —CH₂COOH, —CH₂CH₂Cl, —CH═CH₂, —CH₂CH(OH)₂, and salts thereof;wherein each R₂ is independently selected from C₁₋₁₈ alkyl, aryl,substituted aryl, and substituted alkyl.

In another aspect, the invention relates to an aqueous laundry carecomposition comprising a laundry care ingredient and from 0.0001 wt % to1.0 wt % of a polymeric thiophene hueing agent having the structure ofFormula I:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 5 polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers repeating units; whereineach R₁ is independently selected from H, and C₁₋₄ alkyl.

In a further aspect, the invention relates to an aqueous laundry carecomposition comprising a laundry care ingredient and from 0.0001 wt % to1.0 wt % of a polymeric thiophene hueing agent having the structure ofFormula II:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 5 polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers repeating units.

In yet a further aspect, the invention relates to a method for making anamide-containing, polymeric thiophene hueing agent, wherein the amide isformed via hydrolysis of a nitrile under basic conditions, such as pH>9.

In another aspect, the invention relates to a laundry care compositioncomprising: (1) a laundry care ingredient; (2) from 0.0001 wt % to 1.0wt % of a polymeric thiophene hueing agent having the structure ofFormula I:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers; wherein each R₁ isindependently selected from H, C₁₋₄ alkyl, alkoxy alkyl, halogens, aryl,substituted alkyl or substituted aryl, —COR₂, —CH₂COH, —COOR₂, —COOH,—SO₃H, —CH₂COOH, —CH₂CH₂Cl, —CH═CH₂, —CH₂CH(OH)₂, and salts thereof;wherein each R₂ is independently selected from C₁₋₁₈ alkyl, aryl,substituted aryl, and substituted alkyl; and (3) from 0.0001 wt % to 1.0wt % of a polymeric thiophene hueing agent having the structure ofFormula X:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers; wherein each R₁ isindependently selected from H, C₁₋₄ alkyl, alkoxy alkyl, halogens, aryl,substituted alkyl or substituted aryl, —COR₂, —CH₂COH, —COOR₂, —COOH,—SO₃H, —CH₂COOH, —CH₂CH₂Cl, —CH═CH₂, —CH₂CH(OH)₂, and salts thereof;wherein each R₂ is independently selected from C₁₋₁₈ alkyl, aryl,substituted aryl, and substituted alkyl.

In a further aspect, the invention relates to a laundry care compositioncomprising: (i) a laundry care ingredient; and (ii) from 0.0001 wt % to1.0 wt % of a polymeric thiophene hueing agent having the structure ofFormula I:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers; wherein each R₁ isindependently selected from H, C₁₋₄ alkyl, alkoxy alkyl, halogens, aryl,substituted alkyl or substituted aryl, —COR₂, —CH₂COH, —COOR₂, —COOH,—SO₃H, —CH₂COOH, —CH₂CH₂Cl, —CH═CH₂, —CH₂CH(OH)₂, and salts thereof;wherein each R₂ is independently selected from C₁₋₁₈ alkyl, aryl,substituted aryl, and substituted alkyl; and wherein the laundry carecomposition imparts a whitening effect to a cellulose-containing textilearticle that is measurably greater than a polyester-containing textilearticle treated with the laundry care composition, wherein the whiteningeffect is measured via a whiteness index on each textile article.

In another aspect, the invention relates to a process for measurablyimproving a whitening effect on cellulose-containing textile articles,wherein the improvement is present in an amount that is greater than theamount observed on polyester-containing textile articles, wherein theprocess comprises the following steps: (a) providing acellulose-containing textile substrate, (b) providing apolyester-containing textile substrate, (c) exposing the textilesubstrates of steps (a) and (b) to a laundry care composition comprisedof: (i) a laundry care ingredient; and (ii) from 0.0001 wt % to 1.0 wt %of a polymeric thiophene hueing agent having the structure of Formula I:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers; wherein each R₁ isindependently selected from H, C₁₋₄ alkyl, alkoxy alkyl, halogens, aryl,substituted alkyl or substituted aryl, —COR₂, —CH₂COH, —COOR₂, —COOH,—SO₃H, —CH₂COOH, —CH₂CH₂Cl, —CH═CH₂, —CH₂CH(OH)₂, and salts thereof;wherein each R₂ is independently selected from C₁₋₁₈ alkyl, aryl,substituted aryl, and substituted alkyl; and (d) measuring the whiteningeffect via evaluation of the whiteness index of each textile article.

In another aspect, the invention relates to a textile article, whereinthe textile article contains: (a) a majority by weight of cellulosefiber, and (b) a laundry care composition comprising: (i) a laundry careingredient; and (ii) from 0.0001 wt % to 1.0 wt % of a polymericthiophene hueing agent having the structure of Formula III:

DETAILED DESCRIPTION

The invention described herein is laundry care composition comprising alaundry care ingredient and a polymeric thiophene hueing agent. In oneaspect of the invention, the polymeric thiophene hueing agent is addedto a textile article via a laundry care composition during a standardlaundering process. The laundry care composition that contains thepolymeric thiophene hueing agent is added to a washing machine, therebyallowing the molecule to come into direct contact with the textilearticle. Thus, during the laundry process, the polymeric thiophenehueing agent is deposited onto at least one surface of the textilearticle and improvement in whitening of the treated textile article isachieved.

As used herein, the term “alkoxy” is intended to include C₁-C₈ alkoxyand alkoxy derivatives of polyols having repeating units such asbutylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, unless otherwise specified, the terms “alkyl” and “alkylcapped” are intended to include C₂ to C₁₀₀ alkyl groups, C₂ to C₅₀ alkylgroups, C₅-C₂₅ alkyl groups, or even C₁₀-C₂₀ alkyl groups.

As used herein, unless otherwise specified, the term “aryl” is intendedto include C₆-C₁₂ aryl groups.

As used herein, unless otherwise specified, the term “arylalkyl” isintended to include C₁-C₁₈ alkyl groups and, in one aspect, C₁-C₆ alkylgroups.

As used herein, unless otherwise specified, the term “alkanoyl” refersto univalent groups of the formula —C(O)R^(a), where R^(a) is an alkylgroup, preferably a C₃-C₂₉ alkyl group.

As used herein, unless otherwise specified, the term “alkenyl” refers tounivalent groups derived from acyclic olefinic hydrocarbons by removalof a hydrogen atom from any carbon atom. In the context of thisdefinition, the term “acyclic olefinic hydrocarbons” refers to acyclichydrocarbons containing one or more carbon-carbon double bonds.

The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” maybe shown herein by their typical designation of “EO,” “PO” and “BO,”respectively.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

Polymeric thiophene hueing agents suitable for use in the presentinvention may contain various groups, such as oxyalkylated, acylated,alkylated, carbonylated, olefiniated, and the like, derivatives thereof,prepared by introducing such groups individually, alternatively, and/orin combination, including for example, derivatives prepared by varyingthe order of adding such groups, by increasing the number and order ofadding such groups, and the like.

In one aspect, the invention is an aqueous laundry care compositioncomprising a laundry care ingredient and from 0.0001 wt % to 1.0 wt % ofa polymeric thiophene hueing agent having the structure of Formula I:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers; wherein each R₁ isindependently selected from H, C₁₋₄ alkyl, alkoxy alkyl, halogens, aryl,substituted alkyl or substituted aryl, —COR₂, —CH₂COH, —COOR₂, —COOH,—SO₃H, —CH₂COOH, —CH₂CH₂Cl, —CH═CH₂, —CH₂CH(OH)₂, and salts thereof;wherein each R₂ is independently selected from C₁₋₁₈ alkyl, aryl,substituted aryl, and substituted alkyl.

In a further aspect, the invention is an aqueous laundry carecomposition comprising a laundry care ingredient and from 0.0001 wt % to1.0 wt % of a polymeric thiophene hueing agent having the structure ofFormula I:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 5 polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers repeating units; whereineach R₁ is independently selected from H, and C₁₋₄ alkyl.

In yet a further aspect, the invention is an aqueous laundry carecomposition comprising a laundry care ingredient and from 0.0001 wt % to1.0 wt % of a polymeric thiophene hueing agent having the structure ofFormula II:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 5 polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers repeating units.

The polymeric thiophene hueing agent may be present in the laundry carecomposition in an amount in the range from 1 ppm to 10000 ppm, or in anamount in the range from 1 ppm to 500 ppm.

The laundry care composition may contain water in an amount in the rangefrom 3% to 97% based on total laundry care composition weight, or in therange from 10% to 90% based on total laundry care composition weight, oreven in the range from 25% to 75% based on total laundry carecomposition weight.

The aqueous laundry care composition of the present invention may bepresent in liquid form, in unit dose form, or in a multi-compartmentunit dose form.

Impurities in the hueing agent may also be present. One skilled in theart would recognize that impurities related to regioisomers, incompletereaction, or double coupling of the diazonium salt to the coupler mayresult when making an azo dye. Impurities may include, for example,carboxylic acids, bis-amides, regioisomeric amides or mixtures ofcarboxylic acids, esters, nitriles and amides present in the thiophenemoiety. Thus, the aqueous laundry care composition may further containat least one of the following structures, or salts thereof:

In one aspect of the invention, the aqueous laundry care compositioncontains a laundry care ingredient selected from the group consisting ofcationic polymers, surfactants, builders, chelating agents, dye transferinhibiting agents, dispersants, enzymes, and enzyme stabilizers,catalytic materials, bleach activators, hydrogen peroxide, sources ofhydrogen peroxide, preformed peracids, polymeric dispersing agents, claysoil removal/anti-redeposition agents, brighteners, suds suppressors,dyes, pigments, coloring agents, perfumes, perfume delivery systems,structure elasticizing agents, fabric softeners, carriers, hydrotropes,and processing aids.

A textile article may be treated with the laundry care composition ofthe present invention. As a result, the treated textile article maycontain the polymeric thiophene hueing agent as described herein. In oneaspect of the invention, the textile article is comprised ofcellulose-containing fiber. The textile article may be in the form of afabric. Thus, the invention includes a cellulose-containing fabriccontaining the polymeric thiophene hueing agent as described herein.

A method of treating a textile article to improve the visual appearanceof the article includes the steps of: (1) providing a textile article,and (2) exposing the textile article to the laundry care compositioncontaining the polymeric thiophene hueing agent as described herein. Amethod of treating a textile article may further comprise the steps of(i) treating a textile article with the aqueous or non-aqueous laundrycare composition as described herein, and (ii) rinsing and drying thetreated textile article. The method of treating a textile article withthe laundry care composition of the present invention, whether aqueousor non-aqueous, may be bleach-free.

A method for making an amide-containing, polymeric thiophene hueingagent of the present invention may include forming the amide viahydrolysis of a nitrile group under basic conditions, such as conditionswherein the pH >9. Basic conditions may be formed in the presence of atleast one of carbonates, bicarbonates, amines, hydroxides, alkoxides,and mixtures thereof.

The aqueous laundry care composition containing the polymeric thiophenehueing agent may impart a desired hue to a textile article with arelative hue angle >270, or a relative hue angle in the range from 270to 310, or a relative hue angle in the range from 290 to 310.

In yet another aspect of the invention, there is a laundry carecomposition comprising: (1) a laundry care ingredient; (2) from 0.0001wt % to 1.0 wt % of a polymeric thiophene hueing agent having thestructure of Formula I:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers; wherein each R₁ isindependently selected from H, C₁₋₄ alkyl, alkoxy alkyl, halogens, aryl,substituted alkyl or substituted aryl, —COR₂, —CH₂COH, —COOR₂, —COOH,—SO₃H, —CH₂COOH, —CH₂CH₂Cl, —CH═CH₂, —CH₂CH(OH)₂, and salts thereof;wherein each R₂ is independently selected from C₁₋₁₈ alkyl, aryl,substituted aryl, and substituted alkyl; and (3) from 0.0001 wt % to 1.0wt % of a polymeric thiophene hueing agent having the structure ofFormula X:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers; wherein each R₁ isindependently selected from H, C₁₋₄ alkyl, alkoxy alkyl, halogens, aryl,substituted alkyl or substituted aryl, —COR₂, —CH₂COH, —COOR₂, —COOH,—SO₃H, —CH₂COOH, —CH₂CH₂Cl, —CH═CH₂, —CH₂CH(OH)₂, and salts thereof;wherein each R₂ is independently selected from C₁₋₁₈ alkyl, aryl,substituted aryl, and substituted alkyl.

In a further aspect of the invention, there is a laundry carecomposition comprising: (1) a laundry care ingredient; (2) from 0.0001wt % to 1.0 wt % of a polymeric thiophene hueing agent having thestructure of Formula III:

and (3) from 0.0001 wt % to 1.0 wt % of a polymeric thiophene hueingagent having the structure of Formula Y:

Each polymeric thiophene hueing agent is independently present in thecomposition in an amount in the range from 1 ppm to 10000 ppm, or evenin an amount in the range from 1 ppm to 500 ppm. The polymeric thiophenehueing agents of Formula I and the polymeric thiophene hueing agent ofFormula X are present in a ratio from 1:200 to 200:1, in a ratio from1:100 to 100:1, or even in a ratio from 1:3 to 3:1. In another aspect ofthe invention, the polymeric thiophene hueing agents of Formula III andthe polymeric thiophene hueing agent of Formula Y are present in a ratiofrom 1:200 to 200:1, in a ratio from 1:100 to 100:1, or even in a ratiofrom 1:3 to 3:1.

The laundry care composition may be present in powder form, in liquidform, in unit dose form, or in a multi-compartment unit dose form.

Impurities in the hueing agent may also be present. Impurities mayinclude, for example, carboxylic acids, bis-amides, regioisomeric amidesor mixtures of carboxylic acids, esters, nitriles and amides present inthe thiophene moiety. Thus, the aqueous laundry care composition mayfurther contain at least one of the following structures, or saltsthereof:

The laundry care ingredient may be selected from the group consisting ofcationic polymers, surfactants, builders, chelating agents, dye transferinhibiting agents, dispersants, enzymes, and enzyme stabilizers,catalytic materials, bleach activators, hydrogen peroxide, sources ofhydrogen peroxide, preformed peracids, polymeric dispersing agents, claysoil removal/anti-redeposition agents, brighteners, suds suppressors,dyes, pigments, coloring agents, perfumes, perfume delivery systems,structure elasticizing agents, fabric softeners, carriers, hydrotropes,and processing aids.

The laundry care composition may impart a desired hue to a textilearticle treated therewith having a relative hue angle in the range from210 to 345, or in the range from 270 to 300.

A further aspect of the present invention includes a laundry carecomposition comprising: (i) a laundry care ingredient; and (ii) from0.0001 wt % to 1.0 wt % of a polymeric thiophene hueing agent having thestructure of Formula I:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers; wherein each R₁ isindependently selected from H, C₁₋₄ alkyl, alkoxy alkyl, halogens, aryl,substituted alkyl or substituted aryl, —COR₂, —CH₂COH, —COOR₂, —COOH,—SO₃H, —CH₂COOH, —CH₂CH₂Cl, —CH═CH₂, —CH₂CH(OH)₂, and salts thereof;wherein each R₂ is independently selected from C₁₋₁₈ alkyl, aryl,substituted aryl, and substituted alkyl; and wherein the laundry carecomposition imparts a whitening effect to a cellulose-containing textilearticle that is measurably greater than a polyester-containing textilearticle treated with the laundry care composition, wherein the whiteningeffect is measured via a whiteness index on each textile article.

The polymeric thiophene hueing agent may be present in an amount in therange from 1 ppm to 10000 ppm, or in an amount in the range from 1 ppmto 500 ppm.

The cellulose-containing textile article may exhibit a whitening effectthat is at least two times greater than a polyester-containing textilesubstrate treated with the laundry care composition. Thecellulose-containing textile article may further exhibit a whiteningeffect that is at least five times greater than a polyester-containingtextile substrate treated with the laundry care composition.

The polymeric thiophene hueing agent also provides a whitening bias on acellulose-containing textile article when compared to apolyester-containing textile article, wherein the whitening bias ismeasured via the following formula: whitening bias=(change in whitenessof a cellulose-containing textile article/change in whiteness of apolyester-containing textile article), wherein the whitening effect ismeasured via the whiteness index of each textile article.

The cellulose-containing textile article may be comprised of fiberselected from the group consisting of cotton, linen, rayon, jute, hemp,bamboo, and blends thereof. The cellulose-containing textile article maybe comprised of a majority by weight of cotton fiber. Thecellulose-containing textile article may be comprised of 100% cottonfiber. The polyester-containing textile article may be comprised of amajority by weight of polyester fiber. The polyester-containing textilearticle may be comprised of 100% polyester fiber.

The presence of Formula I provides a hue to the cellulose-containingtextile article, wherein hue is determined via measurement of relativehue angle. The cellulose-containing textile article treated with thelaundry care composition of the present invention may exhibit a relativehue angle in the range from 280 to 345, or in the range from 290 to 320.

Impurities in the hueing agent may also be present. Impurities mayinclude, for example, carboxylic acids, bis-amides, regioisomeric amidesor mixtures of carboxylic acids, esters, nitriles and amides present inthe thiophene moiety. Thus, the aqueous laundry care composition mayfurther contain at least one of the following structures, or saltsthereof:

The laundry care ingredient may be selected from the group consisting ofcationic polymers, surfactants, builders, chelating agents, dye transferinhibiting agents, dispersants, enzymes, and enzyme stabilizers,catalytic materials, bleach activators, hydrogen peroxide, sources ofhydrogen peroxide, preformed peracids, polymeric dispersing agents, claysoil removal/anti-redeposition agents, brighteners, suds suppressors,dyes, pigments, coloring agents, perfumes, perfume delivery systems,structure elasticizing agents, fabric softeners, carriers, hydrotropes,and processing aids.

The present invention also encompasses a method of increasing thewhitening effect/index on a textile article comprising the steps of (i)treating the textile article with the laundry care composition asdescribed herein, and (ii) rinsing and drying the treated textilearticle. The step of treating the textile article may be bleach-free.

Also encompassed herein is a process for measurably improving awhitening effect on cellulose-containing textile articles, wherein theimprovement is present in an amount that is greater than the amountobserved on polyester-containing textile articles, wherein the processcomprises the following steps: (a) providing a cellulose-containingtextile substrate, (b) providing a polyester-containing textilesubstrate, (c) exposing the textile substrates of steps (a) and (b) to alaundry care composition comprised of: (i) a laundry care ingredient;and (ii) from 0.0001 wt % to 1.0 wt % of a polymeric thiophene hueingagent having the structure of Formula I:

wherein each A is independently selected from the group consisting ofpolyethyleneoxy, polypropyleneoxy, and polyethyleneoxy/polypropyleneoxycopolymers, and wherein each A is independently present in the rangefrom 1 to 20 repeating units of polyethyleneoxy, polypropyleneoxy orpolyethyleneoxy/polypropyleneoxy copolymers; wherein each R₁ isindependently selected from H, C₁₋₄ alkyl, alkoxy alkyl, halogens, aryl,substituted alkyl or substituted aryl, —COR₂, —CH₂COH, —COOR₂, —COOH,—SO₃H, —CH₂COOH, —CH₂CH₂Cl, —CH═CH₂, —CH₂CH(OH)₂, and salts thereof;wherein each R₂ is independently selected from C₁₋₈ alkyl, aryl,substituted aryl, and substituted alkyl; and (d) measuring the whiteningeffect via evaluation of the whiteness index of each textile article.

In another aspect of the invention there is a textile article, whereinthe textile article contains: (a) a majority by weight of cellulosefiber, and (b) a laundry care composition comprising: (i) a laundry careingredient; and (ii) from 0.0001 wt % to 1.0 wt % of a polymericthiophene hueing agent having the structure of Formula III:

In one aspect of the invention, the polymeric thiophene hueing agent cancomprise any suitable alkyleneoxy group. Suitable alkyleneoxy groupsinclude those of Formula (C) below:

In the structure of Formula (C) and the other alkyleneoxy structuresthat follow, the carbon atom bonded to R¹⁰¹ is also bonded to thenitrogen atom of the amine group. In the structure of Formula (C), eachR¹⁰¹ and R¹⁰² group is independently selected from the group consistingof hydrogen, alkyl, aryl, alkoxyalkyl, and aryloxyalkyl. R¹⁰⁵ is aterminal group for the oxyalkylene and can be selected from the groupconsisting of hydrogen, alkyl groups (e.g., C₁-C₄ alkyl groups), andaryl groups, with hydrogen being preferred. Preferably, each R¹⁰¹ andR¹⁰² group is independently selected from the group consisting ofhydrogen and alkyl (e.g., C₁-C₄ alkyl). The variable a is an integerequal to or greater than 1 (e.g., from 1 to about 100). For each monomerunit in the alkyleneoxy group, the R¹⁰¹ and R¹⁰² groups areindependently selected from the recited group. Thus, when the variable ais greater than 1, the alkyleneoxy group can be comprised of two or moremonomer units covalently bonded to form the alkyleneoxy group, or eventhree or more monomer units. When the alkyleneoxy group comprises two ormore monomer units (or even three or more monomer units), these monomerunits can be arranged in either a block configuration or in a randomconfiguration, but a block configuration generally is more preferred. Ina preferred embodiment, the alkyleneoxy group comprises monomer unitsindependently selected from the group consisting of ethyleneoxy,propyleneoxy, and butyleneoxy. A suitable example of such an alkyleneoxygroup is Formula (CI) below:

In the structure of Formula (CI), the variables x, y, and z areindependently selected from the group consisting of zero and positiveintegers (e.g., positive integers from 1 to about 100). Preferably, thesum of x, y, and z is 2 or more or 3 or more (e.g., 2 to about 300, 3 toabout 300, 2 to about 200, 3 to about 200, 2 to about 100, 3 to about100, 2 to about 50, 3 to about 50, 2 to about 30, 3 to about 30, 2 toabout 25, 3 to about 25, 2 to about 20, 3 to about 20, 2 to about 15, 3to about 15, 2 to about 10, or 3 to about 10). R¹⁰⁵ is a terminal groupfor the oxyalkylene and can be selected from the group consisting ofhydrogen, alkyl groups (e.g., C₁-C₄ alkyl groups), and aryl groups, withhydrogen being preferred. In certain possibly preferred embodiments, thealkyleneoxy group comprises ethyleneoxy and propyleneoxy monomer unitsarranged in a block configuration. Suitable examples of such alkyleneoxygroups include those of Formulae (CII) and (CIII) below

In the structures of Formulae (CII) and (CIII), the variables, t, u, v,q, r, and s are independently selected from the group consisting of zeroand positive integers (e.g., positive integers from 1 to about 100).Preferably, the sum of t, u, and v and q, r, and s is 2 or more or 3 ormore (e.g., 2 to about 300, 3 to about 300, 2 to about 200, 3 to about200, 2 to about 100, 3 to about 100, 2 to about 50, 3 to about 50, 2 toabout 30, 3 to about 30, 2 to about 25, 3 to about 25, 2 to about 20, 3to about 20, 2 to about 15, 3 to about 15, 2 to about 10, or 3 to about10). R¹⁰⁵ is a terminal group for the oxyalkylene and can be selectedfrom the group consisting of hydrogen, alkyl groups (e.g., C₁-C₄ alkylgroups), and aryl groups, with hydrogen being preferred.

Alkoxylation is carried out by procedures well-known to those skilled inthe art (see, for example, U.S. Pat. Nos. 4,137,243; 5,082,938;5,135,972; 5,591,833; 6,593,483; 7,587,857; 9,056,963; and 9,068,081).Suitable C₁-C₈ alkoxy or alkoxy derivative of polyol having repeatingunits include alkylene oxides. Alkylene oxides may be selected from thegroup consisting of ethylene oxide, propylene oxide, butylene oxide, andmixtures thereof. Alkylene oxide groups may be in the form of polymericchains known as polyalkyleneoxy chains. The term “polyalkyleneoxy,” asused herein, generally refers to molecular structures containing thefollowing repeating units: —CH₂CH₂O—, CH₂CH₂CH₂O—, —CH₂CH₂CH₂CH₂O—,—CH₂CH(CH₃)O—, —CH₂CH(CH₂CH₃)O— CH₂CH₂CH(CH₃)O—, and any combinationsthereof. Typical of such groups are the polymeric epoxides, such as thepolyalkylene oxides and copolymers thereof. Typical polyalkylene oxidesand copolymers of same include those made from alkylene oxide monomerscontaining from two to twenty carbon atoms, or more preferably, from twoto six carbon atoms. Examples include: polyethylene oxides;polypropylene oxides; polybutylene oxides; oxetanes; tetrahydrafurans;copolymers of polyethylene oxides, polypropylene oxides and polybutyleneoxides; and other copolymers including block copolymers, in which amajority of the polymeric substituent is polyethylene oxide,polypropylene oxide and/or polybutylene oxide. Further, suchpolyalkyleneoxy group may have an average molecular weight in the rangeof from about 132 to about 10,000, preferably from about 176 to about5000.

Typically, the alkoxy molecules form caps for the ends of the chainscomprising the polymeric thiophene hueing agent. Thus, the resultingalkoxylated polymeric thiophene hueing agent may have an average degreeof alkoxylation of from 0.5 to 50, or from 1 to 50, or from 1 to 30, orfrom 1 to 20, or from 1 to 10, or from 2 to 50, or from 2 to 30, or from2 to 20, or from 2 to 10, or from 3 to 50 or from 3 to 30, or from 3 to20, or from 3 to 10, or from 4 to 50, or from 4 to 30, or from 4 to 20,or from 4 to 10.

Textile substrates treated with the laundry care composition(s)comprised of the polymeric thiophene hueing agent(s) of the presentinvention may be comprised of synthetic fibers, natural fibers, orcombinations of synthetic and natural fibers. Synthetic fibers include,for example, polyester, acrylic, polyamide, polyolefin, polyaramid,polyurethane, regenerated cellulose (i.e., rayon), and blends thereof.The term “polyamide” is intended to describe any long-chain polymerhaving recurring amide groups (—NH—CO—) as an integral part of thepolymer chain. Examples of polyamides include nylon 6; nylon 6, 6; nylon1, 1; and nylon 6, 10. The term “polyester” is intended to describe anylong-chain polymer having recurring ester groups (—C(O)—O—). Examples ofpolyesters include aromatic polyesters, such as polyethyleneterephthalate (PET), polybutylene terephthalate (PBT), polytrimethyleneterephthalate (PTT), and polytriphenylene terephthalate, and aliphaticpolyesters, such as polylactic acid (PLA). “Polyolefin” includes, forexample, polypropylene, polyethylene, and combinations thereof.“Polyaramid” includes, for example, poly-p-phenyleneteraphthalamid(i.e., Kevlar®), poly-m-phenyleneteraphthalamid (i.e., Nomex®), andcombinations thereof. Natural fibers include, for example, wool, cotton,flax, and blends thereof.

The textile substrate may be formed from fibers or yarns of any size,including microdenier fibers and yarns (fibers or yarns having less thanone denier per filament). The fibers or yarns may have deniers thatrange from less than about 1 denier per filament to about 2000 denierper filament or more preferably, from less than about 1 denier perfilament to about 500 denier per filament, or even more preferably, fromless than about 1 denier per filament to about 300 denier per filament.

Furthermore, the textile substrate may be partially or wholly comprisedof multi-component or bi-component fibers or yarns, which may besplittable, or which have been partially or fully split, along theirlength by chemical or mechanical action. The textile substrate may becomprised of fibers such as staple fiber, filament fiber, spun fiber, orcombinations thereof.

The textile substrate may be of any variety, including but not limitedto, woven fabric, knitted fabric, nonwoven fabric, or combinationsthereof. The textile substrate may optionally be colored by a variety ofdyeing techniques, such as high temperature jet dyeing with dispersedyes, vat dyeing, thermosol dyeing, pad dyeing, transfer printing,screen printing, or any other technique that is common in the art forcomparable textile products. The yarns or fibers comprising the textilesubstrate may optionally be dyed by suitable methods prior to fabricformation, such as, for instance, by package dyeing or solution dyeing.

Textile substrates include, for example, articles of apparel, such asouterwear (e.g., rainwear), workwear (e.g., uniforms), fashion apparel(e.g., shirts, pants, and other garments); drapery; napery (e.g., tablelinens and napkins); residential upholstery; commercial upholstery;automotive upholstery; wall coverings; floorcovering articles (e.g.,carpets, rugs and mats); human bedding (e.g., mattresses, mattresscovers, and the like); pet bedding; outdoor fabric (e.g., outdoorfurniture, awnings, boat covers, and grill covers); medical dressings(e.g., fabrics for use in wound care); and any other article capable ofpossessing discoloration and wherein it is desirable to control (e.g.prevent, remove, and/or improve) said discoloration.

The polymeric thiophene hueing agent of the present invention may beincorporated into a laundry care composition including but not limitedto laundry detergents and fabric treatment compositions. As used herein,the term “laundry care composition” includes, unless otherwiseindicated, granular, powder, liquid, gel, paste, unit dose bar formand/or flake type washing agents and/or fabric treatment compositions.As used herein, the term “fabric treatment composition” includes, unlessotherwise indicated, fabric softening compositions, fabric enhancingcompositions, fabric freshening compositions, and combinations thereof.Such compositions may be, but need not be, rinse added compositions.

Laundry care compositions of the present invention comprise one or moreof the polymeric thiophene hueing agents and a laundry care ingredient.The polymeric thiophene hueing agent may be added to articles using avariety of application techniques. For application to textile articles,the polymeric thiophene hueing agent is preferably included as anadditive in laundry detergent. Thus, application to the textile articleactually occurs when a consumer adds laundry detergent to a washingmachine. Similarly, rinse added fabric softening (“RAFS”) compositionsare typically added in the rinse cycle, which is after the detergentsolution has been used and replaced with the rinsing solution in typicallaundering processes.

The polymeric thiophene hueing agent may be present in the laundry carecomposition (such as the laundry detergent composition) in an amountfrom about 0.0001% to about 10% by weight of the composition, morepreferably from about 0.0001% to about 5% by weight of the composition,and even more preferably from about 0.0001% to about 1% by weight of thecomposition.

The laundry detergent composition comprises a surfactant in an amountsufficient to provide desired cleaning properties. In one embodiment,the laundry detergent composition comprises, by weight, from about 5% toabout 90% of the surfactant, and more specifically from about 5% toabout 70% of the surfactant, and even more specifically from about 5% toabout 40%. The surfactant may comprise anionic, nonionic, cationic,zwitterionic and/or amphoteric surfactants. In a more specificembodiment, the detergent composition comprises anionic surfactant,nonionic surfactant, or mixtures thereof.

Suitable anionic surfactants useful herein can comprise any of theconventional anionic surfactant types typically used in liquid detergentproducts. These include the alkyl benzene sulfonic acids and their saltsas well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Exemplary anionic surfactants are the alkali metal salts of C₁₀₋₁₆ alkylbenzene sulfonic acids, preferably C₁₁₋₁₄ alkyl benzene sulfonic acids.Preferably the alkyl group is linear and such linear alkyl benzenesulfonates are known as “LAS”. Alkyl benzene sulfonates, andparticularly LAS, are well known in the art. Such surfactants and theirpreparation are described for example in U.S. Pat. Nos. 2,220,099 and2,477,383. Especially preferred are the sodium and potassium linearstraight chain alkylbenzene sulfonates in which the average number ofcarbon atoms in the alkyl group is from about 11 to 14. Sodium C₁₁-C₁₄,e.g., C₁₂, LAS is a specific example of such surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkylsulfate surfactants. Such materials, also known as alkyl ether sulfatesor alkyl polyethoxylate sulfates, are those which correspond to theformula: R′—O—(C₂H₄O)_(n)—SO₃M wherein R′ is a C₈-C₂₀ alkyl group, n isfrom about 1 to 20, and M is a salt-forming cation. In a specificembodiment, R′ is C₁₀-C₁₈ alkyl, n is from about 1 to 15, and M issodium, potassium, ammonium, alkylammonium, or alkanolammonium. In morespecific embodiments, R′ is a C₁₂-C₁₆, n is from about 1 to 6 or evenfrom about 1 to 3 or from about 1 to 1.5 and M is sodium.

The alkyl ether sulfates will generally be used in the form of mixturescomprising varying R′ chain lengths and varying degrees of ethoxylation.Frequently such mixtures will inevitably also contain somenon-ethoxylated alkyl sulfate materials, i.e., surfactants of the aboveethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkylsulfates may also be added separately to the compositions of thisinvention and used as or in any anionic surfactant component which maybe present. Specific examples of non-alkoxylated, e.g., non-ethoxylated,alkyl ether sulfate surfactants are those produced by the sulfation ofhigher C₈-C₂₀ fatty alcohols. Conventional primary alkyl sulfatesurfactants have the general formula: ROSO₃-M⁺ wherein R is typically alinear C₈-C₂₀ hydrocarbyl group, which may be straight chain or branchedchain, and M is a water-solubilizing cation. In specific embodiments, Ris a C₁₀-C₁₅ alkyl, and M is alkali metal, more specifically R isC₁₂-C₁₄ and M is sodium.

Specific, non-limiting examples of anionic surfactants useful hereininclude: a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS); b) C₁₀-C₂₀ primary,branched-chain and random alkyl sulfates (AS); c) C₁₀-C₁₈ secondary(2,3) alkyl sulfates; d) C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S) whereinpreferably x is from 1-30; e) C₁₀-C₁₈ alkyl alkoxy carboxylatespreferably comprising 1-5 ethoxy units; f) mid-chain branched alkylsulfates as discussed in U.S. Pat. Nos. 6,020,303 and 6,060,443; g)mid-chain branched alkyl alkoxy sulfates as discussed in U.S. Pat. Nos.6,008,181 and 6,020,303; h) modified alkylbenzene sulfonate (MLAS) asdiscussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; i)methyl ester sulfonate (MES); and j) alpha-olefin sulfonate (AOS).

Suitable nonionic surfactants useful herein can comprise any of theconventional nonionic surfactant types typically used in liquiddetergent products. These include alkoxylated fatty alcohols and amineoxide surfactants. Preferred for use in the liquid detergent productsherein are those nonionic surfactants which are normally liquid.

Suitable nonionic surfactants for use herein include the alcoholalkoxylate nonionic surfactants. Alcohol alkoxylates are materials whichcorrespond to the general formula: R¹(C_(m)H_(2m)O)_(n)OH wherein R¹ isa C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.Preferably R¹ is an alkyl group, which may be primary or secondary, thatcomprises from about 9 to 15 carbon atoms, more preferably from about 10to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcoholswill also be ethoxylated materials that contain from about 2 to 12ethylene oxide moieties per molecule, more preferably from about 3 to 10or even from about 7 to 9 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol materials useful in the liquid detergentcompositions herein will frequently have a hydrophilic-lipophilicbalance (HLB) which ranges from about 3 to 17. More preferably, the HLBof this material will range from about 6 to 15, most preferably fromabout 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have beenmarketed under the tradenames Neodol and Dobanol by the Shell ChemicalCompany.

Another suitable type of nonionic surfactant useful herein comprises theamine oxide surfactants. Amine oxides are materials which are oftenreferred to in the art as “semi-polar” nonionics. Amine oxides have theformula: R(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂·qH₂O. In this formula, Ris a relatively long-chain hydrocarbyl moiety which can be saturated orunsaturated, linear or branched, and can contain from 8 to 20,preferably from 10 to 16 carbon atoms, and is more preferably C₁₂-C₁₆primary alkyl. R′ is a short-chain moiety, preferably selected fromhydrogen, methyl and —CH₂OH. When x+y+z is different from 0, EO isethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxidesurfactants are illustrated by C₁₂₁4 alkyldimethyl amine oxide.

Non-limiting examples of nonionic surfactants include: a) C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; c) C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block polymerssuch as Pluronic® from BASF; d) C₁₄-C₂₂ mid-chain branched alcohols, BA,as discussed in U.S. Pat. No. 6,150,322; e) C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x if from 1-30, as discussed in U.S.Pat. Nos. 6,153,577, 6,020,303 and 6,093,856; f) Alkylpolysaccharides asdiscussed in U.S. Pat. No. 4,565,647 to Llenado, issued Jan. 26, 1986;specifically alkylpolyglycosides as discussed in U.S. Pat. Nos.4,483,780 and 4,483,779; g) Polyhydroxy fatty acid amides as discussedin U.S. Pat. No. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, andWO 94/09099; and h) ether capped poly(oxyalkylated) alcohol surfactantsas discussed in U.S. Pat. No. 6,482,994 and WO 01/42408.

In the laundry detergent compositions herein, the detersive surfactantcomponent may comprise combinations of anionic and nonionic surfactantmaterials. When this is the case, the weight ratio of anionic tononionic will typically range from 10:90 to 90:10, more typically from30:70 to 70:30.

Cationic surfactants are well known in the art and non-limiting examplesof these include quaternary ammonium surfactants, which can have up to26 carbon atoms. Additional examples include a) alkoxylate quaternaryammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b)dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.6,004,922; c) polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d)cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and e) aminosurfactants as discussed in U.S. Pat. No. 6,221,825 and WO 00/47708,specifically amido propyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants; betaine,including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine,C₈ to C₁₈ (preferably C₁₂ to C₁₈) amine oxides and sulfo and hydroxybetaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate wherethe alkyl group can be C₈ to C₁₈, preferably C₁₀ to C₁₄.

Non-limiting examples of ampholytic surfactants include aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents comprises at least about 8 carbon atoms, typically fromabout 8 to about 18 carbon atoms, and at least one comprises an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column19, lines 18-35, for examples of ampholytic surfactants.

As noted, the compositions may be in the form of a solid, either intablet or particulate form, including, but not limited to particles,flakes, or the like, or the compositions may be in the form of a liquid.The liquid detergent compositions comprise an aqueous, non-surfaceactive liquid carrier. Generally, the amount of the aqueous, non-surfaceactive liquid carrier employed in the compositions herein will beeffective to solubilize, suspend or disperse the composition components.For example, the compositions may comprise, by weight, from about 5% toabout 90%, more specifically from about 10% to about 70%, and even morespecifically from about 20% to about 70% of the aqueous, non-surfaceactive liquid carrier.

The most cost-effective type of aqueous, non-surface active liquidcarrier is, of course, water itself. Accordingly, the aqueous,non-surface active liquid carrier component will generally be mostly, ifnot completely, comprised of water. However, other types ofwater-miscible liquids, such alkanols, diols, other polyols, ethers,amines, and the like, and mixtures thereof, may also be added to liquiddetergent compositions as co-solvents or stabilizers in addition to orin place of water. Accordingly, the aqueous non-surface active liquidcarrier component of the liquid detergent composition will generally bepresent in concentrations ranging from about 5% to about 90% by weightof the composition, more preferably from about 20% to about 70% byweight of the composition.

Detergent compositions may also contain bleaching agents. Suitablebleaching agents include, for example, hydrogen peroxide sources, suchas those described in detail in the herein incorporated Kirk Othmer'sEncyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons),Vol. 4, pp. 271-300 “Bleaching Agents (Survey).” These hydrogen peroxidesources include the various forms of sodium perborate and sodiumpercarbonate, including various coated and modified forms of thesecompounds.

The preferred source of hydrogen peroxide used herein can be anyconvenient source, including hydrogen peroxide itself. For example,perborate, e.g., sodium perborate (any hydrate but preferably the mono-or tetra-hydrate), sodium carbonate peroxyhydrate or equivalentpercarbonate salts, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, or sodium peroxide can be used herein. Also useful aresources of available oxygen such as persulfate bleach (e.g., OXONE,manufactured by DuPont). Sodium perborate monohydrate and sodiumpercarbonate are particularly preferred. Mixtures of any convenienthydrogen peroxide sources can also be used.

A suitable percarbonate bleach comprises dry particles having an averageparticle size in the range from about 500 micrometers to about 1,000micrometers, not more than about 10% by weight of said particles beingsmaller than about 200 micrometers and not more than about 10% by weightof said particles being larger than about 1,250 micrometers. Optionally,the percarbonate can be coated with a silicate, borate or water-solublesurfactants. Percarbonate is available from various commercial sourcessuch as FMC, Solvay and Tokai Denka.

Compositions of the present invention may also comprise as the bleachingagent a chlorine-type bleaching material. Such agents are well known inthe art, and include for example sodium dichloroisocyanurate (“NaDCC”).However, chlorine-type bleaches are less preferred for compositionswhich comprise enzymes.

(a) Bleach Activators—Preferably, the peroxygen bleach component in thecomposition is formulated with an activator (peracid precursor). Theactivator is present at levels of from about 0.01%, preferably fromabout 0.5%, more preferably from about 1% to about 15%, preferably toabout 10%, more preferably to about 8%, by weight of the composition. Ableach activator as used herein is any compound which, when used inconjunction with a hydrogen peroxide, source leads to the in situproduction of the peracid corresponding to the bleach activator. Variousnon-limiting examples of activators are disclosed in U.S. Pat. Nos.5,576,282; 4,915,854 and 4,412,934. See also U.S. Pat. No. 4,634,551 forother typical bleaches and activators useful herein.

Preferred activators are selected from the group consisting oftetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzene-sulphonate(NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C₁₀-OBS),benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (C₈-OBS),perhydrolyzable esters and mixtures thereof, most preferablybenzoylcaprolactam and benzoylvalerolactam. Particularly preferredbleach activators in the pH range from about 8 to about 11 are thoseselected having an OBS or VL leaving group.

Preferred hydrophobic bleach activators include, but are not limited to,nonanoyloxybenzenesulphonate (NOBS); 4-[N-(nonanoyl) aminohexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS), an example ofwhich is described in U.S. Pat. No. 5,523,434;dodecanoyloxybenzenesulphonate (LOBS or C₁₂-OBS);10-undecenoyloxybenzenesulfonate (UDOBS or C₁₁-OBS with unsaturation inthe 10 position); and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those described in U.S. Pat. No.5,998,350 to Burns et al.; U.S. Pat. No. 5,698,504 to Christie et al.;U.S. Pat. No. 5,695,679 to Christie et al.; U.S. Pat. No. 5,686,401 toWilley et al.; U.S. Pat. No. 5,686,014 to Hartshorn et al.; U.S. Pat.No. 5,405,412 to Willey et al.; U.S. Pat. No. 5,405,413 to Willey etal.; U.S. Pat. No. 5,130,045 to Mitchel et al.; and U.S. Pat. No.4,412,934 to Chung et al., and copending patent application Ser. No.08/064,564, all of which are incorporated herein by reference.

The mole ratio of peroxygen source (as AvO) to bleach activator in thepresent invention generally ranges from at least 1:1, preferably fromabout 20:1, more preferably from about 10:1 to about 1:1, preferably toabout 3:1.

Quaternary substituted bleach activators may also be included. Thepresent laundry compositions preferably comprise a quaternarysubstituted bleach activator (QSBA) or a quaternary substituted peracid(QSP, preferably a quaternary substituted percarboxylic acid or aquaternary substituted peroxyimidic acid); more preferably, the former.Preferred QSBA structures are further described in U.S. Pat. No.5,686,015 to Willey et al.; U.S. Pat. No. 5,654,421 to Taylor et al.;U.S. Pat. No. 5,460,747 to Gosselink et al.; U.S. Pat. No. 5,584,888 toMiracle et al.; U.S. Pat. No. 5,578,136 to Taylor et al.; all of whichare incorporated herein by reference.

Highly preferred bleach activators useful herein are amide-substitutedas described in U.S. Pat. Nos. 5,698,504; 5,695,679; and 5,686,014, eachof which are cited herein above. Preferred examples of such bleachactivators include: (6-octanamidocaproyl) oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.

Other useful activators are disclosed in U.S. Pat. Nos. 5,698,504;5,695,679; and 5,686,014, each of which is cited herein above, and inU.S. Pat. No. 4,966,723 to Hodge et al. These activators includebenzoxazin-type activators, such as a C₆H₄ ring to which is fused in the1,2-positions a moiety —C(O)OC(R¹)═N—.

Nitriles, such as acetonitriles and/or ammonium nitriles and otherquaternary nitrogen containing nitriles, are another class of activatorsthat are useful herein. Non-limiting examples of such nitrile bleachactivators are described in U.S. Pat. Nos. 6,133,216; 3,986,972;6,063,750; 6,017,464; 5,958,289; 5,877,315; 5,741,437; 5,739,327;5,004,558; and in EP Nos. 790 244, 775 127, 1 017 773, 1 017 776; and inWO 99/14302, WO 99/14296, WO96/40661, all of which are incorporatedherein by reference.

Depending on the activator and precise application, good bleachingresults can be obtained from bleaching systems having an in-use pH offrom about 6 to about 13, and preferably from about 9.0 to about 10.5.Typically, for example, activators with electron-withdrawing moietiesare used for near-neutral or sub-neutral pH ranges. Alkalis andbuffering agents can be used to secure such pH.

Acyl lactam activators, as described in U.S. Pat. Nos. 5,698,504;5,695,679 and 5,686,014, each of which is cited herein above, are veryuseful herein, especially the acyl caprolactams (see for example WO94-28102 A) and acyl valerolactams (see U.S. Pat. No. 5,503,639 toWilley et al. incorporated herein by reference).

(b) Organic Peroxides, especially Diacyl Peroxides—These are extensivelyillustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol.17, John Wiley and Sons, 1982 at pages 27-90 and especially at pages63-72, all incorporated herein by reference. If a diacyl peroxide isused, it will preferably be one which exerts minimal adverse impact onfabric care, including color care.

(c) Metal-Containing Bleach Catalysts—The compositions and methods ofthe present invention can also optionally include metal-containingbleach catalysts, preferably manganese and cobalt-containing bleachcatalysts.

One type of metal-containing bleach catalyst is a catalyst systemcomprising a transition metal cation of defined bleach catalyticactivity (such as copper, iron, titanium, ruthenium tungsten,molybdenum, or manganese cations), an auxiliary metal cation havinglittle or no bleach catalytic activity (such as zinc or aluminumcations), and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243 to Bragg.

Manganese Metal Complexes—If desired, the compositions herein can becatalyzed by means of a manganese compound. Such compounds and levels ofuse are well known in the art and include, for example, themanganese-based catalysts disclosed in U.S. Pat. Nos. 5,576,282;5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Pat. App.Pub. Nos. 549,271 A1; 549,272 A1; 544,440 A2; and 544,490 A1. Preferredexamples of these catalysts include Mn^(IV)₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(PF₆)₂, Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃,Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆), andmixtures thereof. Other metal-based bleach catalysts include thosedisclosed in U.S. Pat. Nos. 4,430,243 and 5,114,611. The use ofmanganese with various complex ligands to enhance bleaching is alsoreported in the following: U.S. Pat. Nos. 4,728,455; 5,284,944;5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

Cobalt Metal Complexes—Cobalt bleach catalysts useful herein are known,and are described, for example, in U.S. Pat. Nos. 5,597,936; 5,595,967;and 5,703,030; and M. L. Tobe, “Base Hydrolysis of Transition-MetalComplexes”, Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The mostpreferred cobalt catalyst useful herein are cobalt pentaamine acetatesalts having the formula [Co(NH₃)₅OAc] T_(y), wherein “OAc” representsan acetate moiety and “T_(y)” is an anion, and especially cobaltpentaamine acetate chloride, [Co(NH₃)₅OAc]Cl₂; as well as[Co(NH₃)₅OAc](OAc)₂; [Co(NH₃)₅OAc](PF₆)₂; [Co(NH₃)₅OAc](SO₄);[Co(NH₃)₅OAc](BF₄)₂; and [Co(NH₃)₅OAc](NO₃)₂(herein “PAC”).

These cobalt catalysts are readily prepared by known procedures, such astaught for example in U.S. Pat. Nos. 6,302,921; 6,287,580; 6,140,294;5,597,936; 5,595,967; and 5,703,030; in the Tobe article and thereferences cited therein; and in U.S. Pat. No. 4,810,410; J. Chem. Ed.(1989), 66 (12), 1043-45; The Synthesis and Characterization ofInorganic Compounds, W. L. Jolly (Prentice-Hall; 1970), pp. 461-3;Inorg. Chem., 18. 1497-1502 (1979); Inorg. Chem., 21. 2881-2885 (1982);Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960);and Journal of Physical Chemistry, 56, 22-25 (1952).

Transition Metal Complexes of Macropolycyclic Rigid Ligands—Compositionsherein may also suitably include as bleach catalyst a transition metalcomplex of a macropolycyclic rigid ligand. The amount used is acatalytically effective amount, suitably about 1 ppb or more, forexample up to about 99.9%, more typically about 0.001 ppm or more,preferably from about 0.05 ppm to about 500 ppm (wherein “ppb” denotesparts per billion by weight and “ppm” denotes parts per million byweight).

Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which aresuitable for use in the invention compositions can in general includeknown compounds where they conform with the definition herein, as wellas, more preferably, any of a large number of novel compounds expresslydesigned for the present laundry or laundry uses, and are non-limitinglyillustrated by any of the following:

-   Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane    Manganese(II)-   Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane    Manganese(II)-   Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)    Hexafluorophosphate-   Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)    Hexafluorophosphate-   Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane-   Manganese(III) Hexafluorophosphate-   Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)    Tetrafluoroborate-   Dichloro-5,12-dimethyl-1,5,8,12 tetraazabicyclo[6.6.2]hexadecane    Manganese(III) Hexafluorophosphate-   Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(Ill)    Hexafluorophosphate-   Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza bicyclo[6.6.2]hexadecane    Manganese(II)-   Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)-   Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane    Manganese(II)-   Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane    Manganese(II)-   Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane    Manganese(II).

As a practical matter, and not by way of limitation, the compositionsand methods herein can be adjusted to provide on the order of at leastone part per hundred million of the active bleach catalyst species inthe composition comprising a lipophilic fluid and a bleach system, andwill preferably provide from about 0.01 ppm to about 25 ppm, morepreferably from about 0.05 ppm to about 10 ppm, and most preferably fromabout 0.1 ppm to about 5 ppm, of the bleach catalyst species in thecomposition comprising a lipophilic fluid and a bleach system.

(d) Bleach Boosting Compounds—The compositions herein may comprise oneor more bleach boosting compounds. Bleach boosting compounds provideincreased bleaching effectiveness in lower temperature applications. Thebleach boosters act in conjunction with conventional peroxygen bleachingsources to provide increased bleaching effectiveness. This is normallyaccomplished through in situ formation of an active oxygen transferagent such as a dioxirane, an oxaziridine, or an oxaziridinium.Alternatively, preformed dioxiranes, oxaziridines and oxaziridiniums maybe used.

Among suitable bleach boosting compounds for use in accordance with thepresent invention are cationic imines, zwitterionic imines, anionicimines and/or polyionic imines having a net charge of from about +3 toabout −3, and mixtures thereof. These imine bleach boosting compounds ofthe present invention include those of the general structure:

where R¹-R⁴ may be a hydrogen or an unsubstituted or substituted radicalselected from the group consisting of phenyl, aryl, heterocyclic ring,alkyl and cycloalkyl radicals.

Among preferred bleach boosting compounds are zwitterionic bleachboosters, which are described in U.S. Pat. Nos. 5,576,282 and 5,718,614.Other bleach boosting compounds include cationic bleach boostersdescribed in U.S. Pat. Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826;5,482,515; 5,550,256; and WO 95/13351, WO 95/13352, and WO 95/13353.

Peroxygen sources are well-known in the art and the peroxygen sourceemployed in the present invention may comprise any of these well knownsources, including peroxygen compounds as well as compounds, which underconsumer use conditions, provide an effective amount of peroxygen insitu. The peroxygen source may include a hydrogen peroxide source, thein situ formation of a peracid anion through the reaction of a hydrogenperoxide source and a bleach activator, preformed peracid compounds ormixtures of suitable peroxygen sources. Of course, one of ordinary skillin the art will recognize that other sources of peroxygen may beemployed without departing from the scope of the invention. The bleachboosting compounds, when present, are preferably employed in conjunctionwith a peroxygen source in the bleaching systems of the presentinvention.

(e) Preformed Peracids—Also suitable as bleaching agents are preformedperacids. The preformed peracid compound as used herein is anyconvenient compound which is stable and which under consumer useconditions provides an effective amount of peracid or peracid anion. Thepreformed peracid compound may be selected from the group consisting ofpercarboxylic acids and salts, percarbonic acids and salts, perimidicacids and salts, peroxymonosulfuric acids and salts, and mixturesthereof. Examples of these compounds are described in U.S. Pat. No.5,576,282 to Miracle et al.

One class of suitable organic peroxycarboxylic acids have the generalformula:

wherein R is an alkylene or substituted alkylene group containing from 1to about 22 carbon atoms or a phenylene or substituted phenylene group,and Y is hydrogen, halogen, alkyl, aryl, —C(O)OH or —C(O)OOH.

Organic peroxyacids suitable for use in the present invention cancontain either one or two peroxy groups and can be either aliphatic oraromatic. When the organic peroxycarboxylic acid is aliphatic, theunsubstituted peracid has the general formula:

wherein Y can be, for example, H, CH₃, CH₂Cl, C(O)OH, or C(O)OOH; and nis an integer from 0 to 20. When the organic peroxycarboxylic acid isaromatic, the unsubstituted peracid has the general formula:

wherein Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen,C(O)OH or C(O)OOH.

Typical monoperoxy acids useful herein include alkyl and arylperoxyacids such as:

-   -   (i) peroxybenzoic acid and ring-substituted peroxybenzoic acid,        e.g. peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium        salt hexahydrate), and o-carboxybenzamidoperoxyhexanoic acid        (sodium salt);    -   (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy        acids, e.g. peroxylauric acid, peroxystearic acid,        N-nonanoylaminoperoxycaproic acid (NAPCA),        N,N-(3-octylsuccinoyl)aminoperoxycaproic acid (SAPA) and        N,N-phthaloylaminoperoxycaproic acid (PAP);    -   (iii) amidoperoxyacids, e.g. monononylamide of either        peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA).

Typical diperoxyacids useful herein include alkyl diperoxyacids andaryldiperoxyacids, such as:

-   -   (i) 1,12-diperoxydodecanedioic acid;    -   (ii) 1,9-diperoxyazelaic acid;    -   (iii) diperoxybrassylic acid; diperoxysebacic acid and        diperoxyisophthalic acid;    -   (iv) 2-decyldiperoxybutane-1,4-dioic acid;    -   (v) 4,4′-sulfonylbisperoxybenzoic acid.

Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781 toHartman and 4,634,551 to Burns et al.; European Patent Application0,133,354 to Banks et al.; and U.S. Pat. No. 4,412,934 to Chung et al.Sources also include 6-nonylamino-6-oxoperoxycaproic acid as describedin U.S. Pat. No. 4,634,551 to Burns et al. Persulfate compounds such asfor example OXONE, manufactured commercially by E.I. DuPont de Nemoursof Wilmington, DE can also be employed as a suitable source ofperoxymonosulfuric acid. PAP is disclosed in, for example, U.S. Pat.Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757 and 5,132,431.

(f) Photobleaches—Suitable photobleaches for use in the treatingcompositions of the present invention include, but are not limited to,the photobleaches described in U.S. Pat. Nos. 4,217,105 and 5,916,481.

(g) Enzyme Bleaching—Enzymatic systems may be used as bleaching agents.The hydrogen peroxide may also be present by adding an enzymatic system(i.e. an enzyme and a substrate therefore) which is capable ofgenerating hydrogen peroxide at the beginning or during the washingand/or rinsing process. Such enzymatic systems are disclosed in EPPatent Application 91202655.6 filed Oct. 9, 1991.

The present invention compositions and methods may utilize alternativebleach systems such as ozone, chlorine dioxide and the like. Bleachingwith ozone may be accomplished by introducing ozone-containing gashaving ozone content from about 20 to about 300 g/m³ into the solutionthat is to contact the fabrics. The gas:liquid ratio in the solutionshould be maintained from about 1:2.5 to about 1:6. U.S. Pat. No.5,346,588 describes a process for the utilization of ozone as analternative to conventional bleach systems and is herein incorporated byreference.

The detergent compositions of the present invention may also include anynumber of additional optional ingredients. These include conventionallaundry detergent composition components such as non-tinting dyes,detersive builders, enzymes, enzyme stabilizers (such as propyleneglycol, boric acid and/or borax), suds suppressors, soil suspendingagents, soil release agents, other fabric care benefit agents, pHadjusting agents, chelating agents, smectite clays, solvents,hydrotropes and phase stabilizers, structuring agents, dye transferinhibiting agents, opacifying agents, optical brighteners, perfumes andcoloring agents. The various optional detergent composition ingredients,if present in the compositions herein, should be utilized atconcentrations conventionally employed to bring about their desiredcontribution to the composition or the laundering operation. Frequently,the total amount of such optional detergent composition ingredients canrange from about 0.01% to about 50%, more preferably from about 0.1% toabout 30%, by weight of the composition.

The liquid detergent compositions are in the form of an aqueous solutionor uniform dispersion or suspension of surfactant, polymeric thiophenehueing agent, and certain optional other ingredients, some of which maynormally be in solid form, that have been combined with the normallyliquid components of the composition, such as the liquid alcoholethoxylate nonionic, the aqueous liquid carrier, and any other normallyliquid optional ingredients. Such a solution, dispersion or suspensionwill be acceptably phase stable and will typically have a viscositywhich ranges from about 100 to 600 cps, more preferably from about 150to 400 cps. For purposes of this invention, viscosity is measured with aBrookfield LVDV-II+ viscometer apparatus using a #21 spindle.

The liquid detergent compositions herein can be prepared by combiningthe components thereof in any convenient order and by mixing, e.g.,agitating, the resulting component combination to form a phase stableliquid detergent composition. In a preferred process for preparing suchcompositions, a liquid matrix is formed containing at least a majorproportion, and preferably substantially all, of the liquid components,e.g., nonionic surfactant, the non-surface active liquid carriers andother optional liquid components, with the liquid components beingthoroughly admixed by imparting shear agitation to this liquidcombination. For example, rapid stirring with a mechanical stirrer mayusefully be employed. While shear agitation is maintained, substantiallyall of any anionic surfactants and the solid form ingredients can beadded. Agitation of the mixture is continued, and if necessary, can beincreased at this point to form a solution or a uniform dispersion ofinsoluble solid phase particulates within the liquid phase. After someor all of the solid-form materials have been added to this agitatedmixture, particles of any enzyme material to be included, e.g., enzymeprills, are incorporated. As a variation of the composition preparationprocedure hereinbefore described, one or more of the solid componentsmay be added to the agitated mixture as a solution or slurry ofparticles premixed with a minor portion of one or more of the liquidcomponents. After addition of all of the composition components,agitation of the mixture is continued for a period of time sufficient toform compositions having the requisite viscosity and phase stabilitycharacteristics. Frequently this will involve agitation for a period offrom about 30 to 60 minutes.

In an alternate embodiment for forming the liquid detergentcompositions, the polymeric thiophene hueing agent is first combinedwith one or more liquid components to form a polymeric thiophene hueingagent premix, and this premix is added to a composition formulationcontaining a substantial portion, for example more than 50% by weight,more specifically, more than 70% by weight, and yet more specifically,more than 90% by weight, of the balance of components of the laundrydetergent composition. For example, in the methodology described above,both the polymeric thiophene hueing agent premix and the enzymecomponent are added at a final stage of component additions. In afurther embodiment, the polymeric thiophene hueing agent is encapsulatedprior to addition to the detergent composition, the encapsulatedpolymeric thiophene hueing agent is suspended in a structured liquid,and the suspension is added to a composition formulation containing asubstantial portion of the balance of components of the laundrydetergent composition.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing solutions for use in the launderingof textile substrates such as fabrics. Generally, an effective amount ofsuch compositions is added to water, preferably in a conventional fabriclaundering automatic washing machine, to form such aqueous launderingsolutions. The aqueous washing solution so formed is then contacted,preferably under agitation, with the fabrics to be laundered therewith.An effective amount of the liquid detergent compositions herein added towater to form aqueous laundering solutions can comprise amountssufficient to form from about 500 to 7,000 ppm of composition in aqueouswashing solution. More preferably, from about 1,000 to 3,000 ppm of thedetergent compositions herein will be provided in aqueous washingsolution.

Fabric Treatment Compositions/Rinse Added Fabric Softening Compositions

In another specific embodiment, the polymeric thiophene hueing agent ofthe present invention may be included in a fabric treatment composition.The fabric treatment composition may be comprised of at least onepolymeric thiophene hueing agent and a rinse added fabric softeningcomposition (“RAFS;” also known as rinse added fabric conditioningcompositions). Examples of typical rinse added softening compositionscan be found in U.S. Provisional Patent Application Ser. No. 60/687,582filed on Oct. 8, 2004. The rinse added fabric softening compositions ofthe present invention may comprise (a) fabric softening active (“FSA”)and (b) a polymeric thiophene hueing agent. The rinse added fabricsoftening composition may comprise from about 1% to about 90% by weightof the FSA, more preferably from about 5% to about 50% by weight of theFSA. The polymeric thiophene hueing agent may be present in the rinseadded fabric softening composition in an amount from about 0.5 ppb toabout 50 ppm, more preferably from about 0.5 ppm to about 30 ppm.

In one embodiment of the invention, the fabric softening active is aquaternary ammonium compound suitable for softening fabric in a rinsestep. In one embodiment, the FSA is formed from a reaction product of afatty acid and an aminoalcohol obtaining mixtures of mono-, di-, and, inone embodiment, triester compounds. In another embodiment, the FSAcomprises one or more softener quaternary ammonium compounds such, butnot limited to, as a monoalkyquaternary ammonium compound, a diamidoquaternary compound and a diester quaternary ammonium compound, or acombination thereof.

In one aspect of the invention, the FSA comprises a diester quaternaryammonium (hereinafter “DQA”) compound composition. In certainembodiments of the present invention, the DQA compounds compositionsalso encompasses a description of diamido FSAs and FSAs with mixed amidoand ester linkages as well as the aforementioned diester linkages, allherein referred to as DQA.

A first type of DQA (“DQA (1)”) suitable as a FSA includes a compoundcomprising the formula:

{R_(4-m)—N⁺—[(CH₂)_(n)—Y—R¹]_(m)}X⁻

wherein each R substituent is either hydrogen, a short chain C₁-C₆,preferably C₁-C₃ alkyl or hydroxyalkyl group, e.g., methyl (mostpreferred), ethyl, propyl, hydroxyethyl, and the like, poly (C₂₋₃alkoxy), preferably polyethoxy, group, benzyl, or mixtures thereof; eachm is 2 or 3; each n is from 1 to about 4, preferably 2; each Y is—O—(O)C—, —C(O)—O—, —NR—C(O)—, or —C(O)—NR— and it is acceptable foreach Y to be the same or different; the sum of carbons in each R¹, plusone when Y is —O—(O)C— or —NR—C(O)—, is C₁₂-C₂₂, preferably C₁₄-C₂₀,with each R¹ being a hydrocarbyl, or substituted hydrocarbyl group; itis acceptable for R¹ to be unsaturated or saturated and branched orlinear and preferably it is linear; it is acceptable for each R¹ to bethe same or different and preferably these are the same; and X⁻ can beany softener-compatible anion, preferably, chloride, bromide,methylsulfate, ethylsulfate, sulfate, phosphate, and nitrate, morepreferably chloride or methyl sulfate. Preferred DQA compounds aretypically made by reacting alkanolamines such as MDEA(methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Somematerials that typically result from such reactions includeN,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride orN,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium methylsulfatewherein the acyl group is derived from animal fats, unsaturated, andpolyunsaturated, fatty acids, e.g., tallow, hardened tallow, oleic acid,and/or partially hydrogenated fatty acids, derived from vegetable oilsand/or partially hydrogenated vegetable oils, such as, canola oil,safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, talloil, rice bran oil, palm oil, etc.

Non-limiting examples of suitable fatty acids are listed in U.S. Pat.No. 5,759,990 at column 4, lines 45-66. In one embodiment, the FSAcomprises other actives in addition to DQA (1) or DQA. In yet anotherembodiment, the FSA comprises only DQA (1) or DQA and is free oressentially free of any other quaternary ammonium compounds or otheractives. In yet another embodiment, the FSA comprises the precursoramine that is used to produce the DQA.

In another aspect of the invention, the FSA comprises a compound,identified as DTTMAC comprising the formula:

[R_(4-m)—N⁽⁺⁾—R¹ _(m)]A⁻

wherein each m is 2 or 3, each R¹ is a C₆-C₂₂, preferably C₁₄-C₂₀, butno more than one being less than about C₁₂ and then the other is atleast about 16, hydrocarbyl, or substituted hydrocarbyl substituent,preferably C₁₀-C₂₀ alkyl or alkenyl (unsaturated alkyl, includingpolyunsaturated alkyl, also referred to sometimes as “alkylene”), mostpreferably C₁₂-C₁₈ alkyl or alkenyl, and branch or unbranched. In oneembodiment, the Iodine Value (IV) of the FSA is from about 1 to 70; eachR is H or a short chain C₁-C₆, preferably C₁-C₃ alkyl or hydroxyalkylgroup, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, andthe like, benzyl, or (R²O)₂₋₄H where each R² is a C₁₋₆ alkylene group;and A⁻ is a softener compatible anion, preferably, chloride, bromide,methylsulfate, ethylsulfate, sulfate, phosphate, or nitrate; morepreferably chloride or methyl sulfate.

Examples of these FSAs include dialkydimethylammonium salts anddialkylenedimethylammonium salts such as ditallowdimethylammonium andditallowdimethylammonium methylsulfate. Examples of commerciallyavailable dialkylenedimethylammonium salts usable in the presentinvention are di-hydrogenated tallow dimethyl ammonium chloride andditallowdimethyl ammonium chloride available from Degussa under thetrade names Adogen® 442 and Adogen® 470 respectively. In one embodiment,the FSA comprises other actives in addition to DTTMAC. In yet anotherembodiment, the FSA comprises only compounds of the DTTMAC and is freeor essentially free of any other quaternary ammonium compounds or otheractives.

In one embodiment, the FSA comprises an FSA described in U.S. Pat. Pub.No. 2004/0204337 A1, published Oct. 14, 2004 to Corona et al., fromparagraphs 30-79. In another embodiment, the FSA is one described inU.S. Pat. Pub. No. 2004/0229769 A1, published Nov. 18, 2005, to Smith etal., on paragraphs 26-31; or U.S. Pat. No. 6,494,920, at column 1, line51 et seq. detailing an “esterquat” or a quaternized fatty acidtriethanolamine ester salt.

In one embodiment, the FSA is chosen from at least one of the following:ditallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methylsulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, orcombinations thereof.

In one embodiment, the FSA may also include amide containing compoundcompositions. Examples of diamide comprising compounds may include butnot limited to methyl-bis(tallowamidoethyl)-2-hydroxyethylammoniummethyl sulfate (available from Degussa under the trade names Varisoft110 and Varisoft 222). An example of an amide-ester containing compoundisN-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N-methylamine.

Another specific embodiment of the invention provides for a rinse addedfabric softening composition further comprising a cationic starch.Cationic starches are disclosed in US 2004/0204337 A1. In oneembodiment, the rinse added fabric softening composition comprises fromabout 0.1% to about 7% of cationic starch by weight of the fabricsoftening composition. In one embodiment, the cationic starch is HCP401from National Starch.

Suitable Laundry Care Ingredients

While not essential for the purposes of the present invention, thenon-limiting list of laundry care ingredients illustrated hereinafterare suitable for use in the laundry care compositions and may bedesirably incorporated in certain embodiments of the invention, forexample to assist or enhance performance, for treatment of the substrateto be cleaned, or to modify the aesthetics of the composition as is thecase with perfumes, colorants, dyes or the like. It is understood thatsuch ingredients are in addition to the components that were previouslylisted for any particular embodiment. The total amount of such adjunctsmay range from about 0.1% to about 50%, or even from about 1% to about30%, by weight of the laundry care composition.

The precise nature of these additional components, and levels ofincorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which it is to be used.Suitable laundry care ingredients include, but are not limited to,polymers, for example cationic polymers, surfactants, builders,chelating agents, dye transfer inhibiting agents, dispersants, enzymes,and enzyme stabilizers, catalytic materials, bleach activators,polymeric dispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfume and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or coloring agents. Inaddition to the disclosure below, suitable examples of such otheradjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282,6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.

As stated, the laundry care ingredients are not essential to Applicants'laundry care compositions. Thus, certain embodiments of Applicants'compositions do not contain one or more of the following adjunctsmaterials: bleach activators, surfactants, builders, chelating agents,dye transfer inhibiting agents, dispersants, enzymes, and enzymestabilizers, catalytic metal complexes, polymeric dispersing agents,clay and soil removal/anti-redeposition agents, brighteners, sudssuppressors, dyes, additional perfumes and perfume delivery systems,structure elasticizing agents, fabric softeners, carriers, hydrotropes,processing aids and/or coloring agents. However, when one or moreadjuncts are present, such one or more adjuncts may be present asdetailed below:

Surfactants—The compositions according to the present invention cancomprise a surfactant or surfactant system wherein the surfactant can beselected from nonionic and/or anionic and/or cationic surfactants and/orampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.The surfactant is typically present at a level of from about 0.1%, fromabout 1%, or even from about 5% by weight of the cleaning compositionsto about 99.9%, to about 80%, to about 35%, or even to about 30% byweight of the cleaning compositions.

Builders—The compositions of the present invention can comprise one ormore detergent builders or builder systems. When present, thecompositions will typically comprise at least about 1% builder, or fromabout 5% or 10% to about 80%, 50%, or even 30% by weight, of saidbuilder. Builders include, but are not limited to, the alkali metal,ammonium and alkanolammonium salts of polyphosphates, alkali metalsilicates, alkaline earth and alkali metal carbonates, aluminosilicatebuilders polycarboxylate compounds. ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether,1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, andcarboxymethyl-oxysuccinic acid, the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylatessuch as mellitic acid, succinic acid, oxydisuccinic acid, polymaleicacid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid,and soluble salts thereof.

Chelating Agents—The compositions herein may also optionally contain oneor more copper, iron and/or manganese chelating agents. If utilized,chelating agents will generally comprise from about 0.1% by weight ofthe compositions herein to about 15%, or even from about 3.0% to about15% by weight of the compositions herein.

Dye Transfer Inhibiting Agents—The compositions of the present inventionmay also include one or more dye transfer inhibiting agents. Suitablepolymeric dye transfer inhibiting agents include, but are not limitedto, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Whenpresent in the compositions herein, the dye transfer inhibiting agentsare present at levels from about 0.0001%, from about 0.01%, from about0.05% by weight of the cleaning compositions to about 10%, about 2%, oreven about 1% by weight of the cleaning compositions.

Dispersants—The compositions of the present invention can also containdispersants. Suitable water-soluble organic materials are the homo- orco-polymeric acids or their salts, in which the polycarboxylic acid maycomprise at least two carboxyl radicals separated from each other by notmore than two carbon atoms.

Enzymes—The compositions can comprise one or more detergent enzymeswhich provide cleaning performance and/or fabric care benefits. Examplesof suitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, keratanases, reductases, oxidases,phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, ß-glucanases, arabinosidases, hyaluronidase,chondroitinase, laccase, and amylases, or mixtures thereof. A typicalcombination is a cocktail of conventional applicable enzymes likeprotease, lipase, cutinase and/or cellulase in conjunction with amylase.

Enzyme Stabilizers—Enzymes for use in compositions, for example,detergents can be stabilized by various techniques. The enzymes employedherein can be stabilized by the presence of water-soluble sources ofcalcium and/or magnesium ions in the finished compositions that providesuch ions to the enzymes.

Catalytic Metal Complexes—Applicants' compositions may include catalyticmetal complexes. One type of metal-containing bleach catalyst is acatalyst system comprising a transition metal cation of defined bleachcatalytic activity, such as copper, iron, titanium, ruthenium, tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methyl-enephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243.

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. Nos. 5,597,936 and 5,595,967. Such cobaltcatalysts are readily prepared by known procedures, such as taught forexample in U.S. Pat. Nos. 5,597,936, and 5,595,967.

Compositions herein may also suitably include a transition metal complexof a macropolycyclic rigid ligand—abbreviated as “MRL”. As a practicalmatter, and not by way of limitation, the compositions and cleaningprocesses herein can be adjusted to provide on the order of at least onepart per hundred million of the benefit agent MRL species in the aqueouswashing medium, and may provide from about 0.005 ppm to about 25 ppm,from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about5 ppm, of the MRL in the wash liquor.

Preferred transition-metals in the instant transition-metal bleachcatalyst include manganese, iron and chromium. Preferred MRL's hereinare a special type of ultra-rigid ligand that is cross-bridged such as5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa-decane. Suitabletransition metal MRLs are readily prepared by known procedures, such astaught for example in WO 00/32601, and U.S. Pat. No. 6,225,464.

Exemplary Laundry Care Composition Formulations:

Liquid Detergent Formulations:

Table A provides examples of liquid detergent formulations which includeat least one polymeric thiophene hueing agent of the present invention.

TABLE A Liquid Detergent Formulations Comprising Polymeric ThiopheneHueing Agent 1a 1b 1c 1d 1e 1f⁴ Ingredient wt % wt % wt % wt % wt % wt %sodium alkyl ether sulfate 14.4% 14.4%  9.2%  5.4% linear alkylbenzenesulfonic  4.4%  4.4% 12.2%  5.7%  1.3% 22.0% acid alkyl ethoxylate  2.2% 2.2%  8.8%  8.1%  3.4% 18.0% amine oxide  0.7%  0.7%  1.5% citric acid 2.0%  2.0%  3.4%  1.9%    1.6% fatty acid  3.0%  3.0%  8.3% 16.0%protease  1.0%  1.0%  0.7%  1.0%  2.5% amylase  0.2%  0.2%  0.2%  0.3%lipase  0.2% borax  1.5%  1.5%  2.4%  2.9% calcium and sodium formate 0.2%  0.2% formic acid  1.1% amine ethoxylate polymers  1.8%  1.8% 2.1%  3.2% sodium polyacrylate  0.2% sodium polyacrylate copolymer 0.6% DTPA¹  0.1%    0.9% DTPMP²  0.3% EDTA³  0.1% fluorescent whiteningagent 0.15% 0.15%  0.2% 0.12% 0.12%  0.2% ethanol  2.5%  2.5%  1.4% 1.5% propanediol  6.6%  6.6%  4.9%  4.0% 15.7% sorbitol  4.0%ethanolamine  1.5%  1.5%  0.8%  0.1% 11.0% sodium hydroxide  3.0%  3.0% 4.9%  1.9%  1.0% sodium cumene sulfonate  2.0% silicone suds suppressor0.01% perfume  0.3%  0.3%  0.7%  0.3%  0.4%  0.6% Polymeric ThiopheneHueing 0.013%  0.001%  0.005%  0.003%  0.0005%  0.001%  Agent waterbalance balance balance balance balance balance  100.0%  100.0%  100.0% 100.0%   100.0%  100.0% ¹diethylenetriaminepentaacetic acid, sodiumsalt ²diethylenetriaminepentakismethylenephosphonic acid, sodium salt³ethylenediaminetetraacetic acid, sodium salt ⁴a compact formula,packaged as a unitized dose in polyvinyl alcohol film

Granular Detergent Formulations:

Table B provides examples of granular detergent formulations whichinclude at least one polymeric thiophene hueing agent of the presentinvention.

TABLE B Granular Detergent Formulations Comprising Polymeric ThiopheneHueing Agent 2a 2b 2c 2d 2e Ingredient wt % wt % wt % wt % wt % Nalinear alkylbenzene sulfonate 3.4% 3.3% 11.0% 3.4% 3.3% Na alkylsulfate4.0% 4.1% 4.0% 4.1% Na alkyl sulfate (branched) 9.4% 9.6% 9.4% 9.6%alkyl ethoxylate 3.5% type A zeolite 37.4% 35.4% 26.8% 37.4% 35.4%sodium carbonate 22.3% 22.5% 35.9% 22.3% 22.5% sodium sulfate 1.0% 18.8%1.0% sodium silicate 2.2% protease 0.1% 0.2% 0.1% 0.2% sodiumpolyacrylate 1.0% 1.2% 0.7% 1.0% 1.2% carboxymethylcellulose 0.1% PEG600 0.5% 0.5% PEG 4000 2.2% 2.2% DTPA 0.7% 0.6% 0.7% 0.6% fluorescentwhitening agent 0.1% 0.1% 0.1% 0.1% 0.1% sodium percarbonate 5.0% 5.0%sodium nonanoyloxybenzenesulfonate 5.3% 5.3% silicone suds suppressor0.02% 0.02% 0.02% 0.02% perfume 0.3% 0.3% 0.2% 0.3% 0.3% PolymericThiophene Hueing Agent 0.004% 0.006% 0.002% 0.004% 0.02% water andmiscellaneous balance balance balance balance balance 100.0% 100.0%100.0% 100.0% 100.0%

Fabric Treatment Compositions:

Table C provides examples of liquid fabric treatment compositions whichinclude at least one polymeric thiophene hueing agent of the presentinvention.

TABLE C Liquid Fabric Treatment Compositions Comprising PolymericThiophene Hueing Agent Ingredients a b c d Fabric Softening Active ^(a)13.70% 13.70% 13.70% 13.70% Ethanol 2.14% 2.14% 2.14% 2.14% CationicStarch ^(b) 2.17% 2.17% 2.17% 2.17% Perfume 1.45% 1.45% 1.45% 1.45%Phase Stabilizing 0.21% 0.21% 0.21% 0.21% Polymer ^(c) Calcium Chloride0.147% 0.147% 0.147% 0.147% DTPA ^(d) 0.007% 0.007% 0.007% 0.007%Preservative ^(e)  5 ppm  5 ppm  5 ppm  5 ppm Antifoam ^(f) 0.015%0.015% 0.015% 0.015% Polymeric Thiophene 30 ppm 30ppm 30ppm 15 ppmHueing Agent Tinopal CBS-X ^(g) 0.2 0.2 0.2 0.2 Ethoquad C/25 ^(h) 0.260.26 0.26 0.26 Ammonium Chloride 0.1% 0.1% 0.1% 0.1% Hydrochloric Acid0.012% 0.012% 0.012% 0.012% Deionized Water Balance Balance BalanceBalance ^(a) N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.^(b) Cationic starch based on common maize starch or potato starch,containing 25% to 95% amylose and a degree of substitution of from 0.02to 0.09, and having a viscosity measured as Water Fluidity having avalue from 50 to 84. ^(c) Copolymer of ethylene oxide and terephthalatehaving the formula described in U.S. Pat. No. 5,574,179 at col. 15,lines 1-5, wherein each X is methyl, each n is 40, u is 4, each R¹ isessentially 1,4-phenylene moieties, each R² is essentially ethylene,1,2-propylene moieties, or mixtures thereof. ^(d)Diethylenetriaminepentaacetic acid. ^(e) KATHON ® CG available from Rohmand Haas Co. ^(f) Silicone antifoam agent available from Dow CorningCorp, under the trade name DC2310. ^(g) Disodium4,4′-bis-(2-sulfostyryl) biphenyl, available from Ciba SpecialtyChemicals. ^(h) Cocomethyl ethoxylated [15] ammonium chloride, availablefrom Akzo Nobel.

EXAMPLES

The following examples further illustrate the subject matter describedabove but, of course, should not be construed as in any way limiting thescope thereof.

Polymeric thiophene hueing agent of Formula I was synthesized and testedfor its deposition during the wash cycle at several concentrations inlaundry detergent and fabric softening compositions. The washings werecarried out for cotton and polyester-containing fabrics. Detailedsynthesis and testing results are reported below in more detail.

Test Procedures:

Method for Determining Relative Hue Angle (vs. AATCC Control) (Ref:WO2019075142A1):

The relative hue angle delivered by a hueing agent to cotton fabricstreated according to Method I described below was determined as follows:

-   -   a) The a* and b* values of the 4 swatches from each solution        were averaged and the following formulas used to determine Aa*        and Ab*

Aa*=a* _(s) −a* _(c) and Ab*=b* _(s) −b* _(c)

-   -   wherein the subscripts c and s respectively refer to the fabric        washed in AATCC heavy duty liquid detergent nil brightener        (control) and the fabric washed in the laundry care formulation        containing the hueing agents (sample).    -   b) If the absolute value of both Aa* and Ab*<0.25, no Relative        Hue Angle (RHA) was calculated. If the absolute value of either        Aa* or Ab* is >0.25, the RHA was determined using one of the        following formulas:

RHA=ATAN 2(Aa*,Ab*) for Ab*>0

RHA=360+ATAN 2(Aa*,Ab*) for Ab*<0.

Method for Determining ΔWI:

The WI CIE values of the swatches for each wash solution was calculatedusing the following equation:

ΔWI=WI CIE (after wash)−WI CIE (before wash).

Method for Calculating ΔE:

L*, a*, b* values were taken and converted into delta E values bycalculating the difference in L, a and b between the after-washmeasurements and those of an identical white cloth which had not beenwashed with hueing agent and then applying the equation:

ΔE=√{square root over (ΔL ² +Δa ² +Δb ²)}.

The bias for cotton is determined by the following equation:

${Bias} = \frac{( {\Delta{WI}{on}{Cotton}} )}{( {\Delta{WI}{on}{PE}} )}$

Method I: Wash Test Method for Determining Whitening

Preparation of Test Fabrics:

Test fabrics (purchased from Testfabrics, Inc.) included a bleachedcotton t-shirt fabric 60″ open width style number 437W-60, texturizedpolyester interlock knit fabric style number 730, and texturized nylon6,6 stretch fabric double knit style number 314. Each sample was cut to16 cm by 16 cm in size. The fabrics were prepared prior to use bywashing one full cycle in AATCC liquid laundry detergent withoutbrighteners and then rinsed twice prior to drying.

Preparation of Wash Water Solution Containing the Hueing Dye:

A sufficient volume of wash water containing liquid or powder detergentwithout brightener was prepared by dissolving the detergent in tap waterat room temperature at a concentration of 1 gram per liter. BothComparative Hueing Agent 1 and Inventive Hueing Agent 1 were then addedto the wash water in amounts to give the same absorptivity in each washsolution. This amount of hueing agent for each experiment corresponds toabout 3 ppm in wash water. For multi-wash experiments, the hueing agentwas present at 1 ppm in wash water.

Wash Procedure:

Washing tests were completed using a tergotometer. A fabric mixture wasused for each wash that was composed of 63% cotton, 25% polyester and12% nylon. Total fabric in wash water corresponded to a 25:1liquor:fabric ratio. Fabrics were agitated at 220 rpm for 15 minutes.After washing, each set of fabrics was rinsed twice with tap water.After rinsing, all fabrics were dried in a dryer for one hour. Afterdrying, the fabric samples were read using an X-Rite Color i7spectrophotometer. The average reflectance of all samples for eachfabric type at each wash condition was used to calculate L*, a*, b*, andWI-CIE values.

Example 1

A polymeric thiophene hueing agent was made according to the proceduredescribed below.

Comparative Hueing Agent 1, prepared with m-toluidine 5EO according toExample 3 of U.S. Pat. No. 4,912,203, was treated under basic conditions(pH >9) to form Inventive Hueing Agent 1. Surprisingly, upon treatingcomparative hueing agent with base, decomposition of the azo colorantwas not observed. Instead, selective hydrolysis of one nitrile bond tothe amide could be achieved to give the Inventive Hueing Agent 1. Thesetwo hueing agents were tested against each other for comparativepurposes.

To a round bottom flask was charged a polyethylene glycol 200 solutioncontaining 13 g of Comparative Hueing Agent 1, prepared according toExample 3 from U.S. Pat. No. 4,912,203 (25 mmol), water (33 mL) and 50%aqueous sodium hydroxide (25 mmol). The pH was >9. The mixture washeated to 90° C. for 1 hour, whereby UPLC analysis showed completion ofthe reaction. The solution was neutralized to a pH of 7 with aceticacid. A reddish-violet solution containing 3.5 wt % of dissolvedInventive Hueing Agent 1 was obtained.

The Inventive Hueing Agent 1 was compared to the Comparative HueingAgent 1 using the test conditions listed above. Table 1 shows theimprovements in whitening and changes in hue angle on both cotton andpolyester fabrics upon treatment with the composition containingInventive Hueing Agent 1 vs Comparative Hueing Agent 1 on cotton fabricat 3 ppm in wash water loading.

TABLE 1 Whitening Effect of Hueing Agents Relative Relative Hue ΔWI onHue Angle ΔWI on Angle on Bias for Hueing Agent Cotton on CottonPolyester Polyester Cotton Comparative 5.9 268 5.4 271 1.09 Hueing Agent1 Inventive 8.6 301 1.7 295 5.06 Hueing Agent 1

Test results on cotton fabric illustrate whitening performance ofInventive Hueing Agent 1 improved almost 3 units over Comparative HueingAgent 1. In addition, the hue angle on the fabric treated with InventiveHueing Agent 1 shifted to a more reddish shade, which in someapplications is preferred by consumers.

When the whitening bias was calculated using the equation above, thewhitening improvement on cotton treated with Inventive Hueing Agent 1was five times that of polyester fabric. In comparison, there was noreal bias when treated with Comparative Hueing Agent 1. Since cottonfabrics tend to yellow over time on exposure to light, air andcontaminants more than synthetic fabrics, the need for a hueing agentthat targets cotton over polyester is very important.

Additionally, the composition containing Inventive Hueing Agent 1 showeda leveling effect, wherein the ΔE of the fabric did not change incomparison to fabric washed without the inventive hueing dye aftermultiple washes. This result indicates that an equilibrium hueing pointwas reached where the amount of dye depositing through subsequent washesis equal to the dye being removed from the fabric in those washes.Therefore, another advantage of the present invention is that an optimumlevel of hueing on the fabric was reached without staining the fabric.Test results are shown in Table 2.

TABLE 2 Multi-Wash Data for Cotton at 1 ppm in Wash Water ΔE* after ΔE*after ΔE* after ΔE* after Hueing Agent 1 wash 3 washes 5 washes 8 washesInventive 1.6 2.9 3.2 3.4 Hueing Agent 1

The effect of whitening was also evaluated using a blend of hueingagents. Fabrics were washed according to the wash method describedherein (at 3 ppm total loading of hueing dyes) with varying ratios ofInventive Hueing Agent 1 to Hueing Agent 2. Hueing Agent 2 isrepresented by Formula Y. Test results are provided in Tables 3 and 4.Test results demonstrate variations in the relative hue angle on thefabric, which may be desirable as different regions in the world have apreference for various hue on fabric. Thus, being able to tune theperceived whitening benefits through adjusting the hue angle isimportant. Test results further illustrate that the ratios of the twohueing agents (Inventive Hueing Agent 1 and Hueing Agent 2) can bevaried to target a desired hue angle between 270 and 300 on both cottonand polyester fabrics. The hueing agents alone may give ranges that areslightly outside of the desired hue angle (dependent on detergent andfabric).

TABLE 3 Relative Hue Angle on Cotton vs Ratio of Hueing Agents at 3 ppmTotal Loading in Wash Water 75% 50% 25% Hueing Hueing Hueing Agent AgentAgent 2:25% 2:50% 2:75% 100% 100% Inventive Inventive InventiveInventive Hueing Hueing Hueing Hueing Hueing Agent 2 Agent 1 Agent 1Agent 1 Agent 1 Relative Hue 274 282 295 299 302 Angle (RHA) from AATCCLiquid Detergent Relative Hue 268 282 293 296 301 Angle (RHA) from AATCCPowder Detergent

TABLE 4 Relative Hue Angle on Polyester vs Ratio of Hueing Agents at 3ppm Total Loading in Wash Water 75% 50% 25% Hueing Hueing Hueing AgentAgent Agent 2:25% 2:50% 2:75% 100% 100% Inventive Inventive InventiveInventive Hueing Hueing Hueing Hueing Hueing Agent 2 Agent 1 Agent 1Agent 1 Agent 1 Relative Hue 276 275 280 281 292 Angle (RHA) from AATCCLiquid Detergent Relative Hue 271 272 274 275 295 Angle (RHA) from AATCCPowder Detergent

Additional testing was performed to compare each of Inventive HueingAgent 1 and Hueing Agent 2 on cotton fabric at 1 ppm loading levels.Test results are provided in Table 5. Test results demonstrate that bothhueing agents build on fabric, as determined by ΔE, but level off aftera certain number of washes. This is advantageous in that the hueingagents will not stain the fabric but will give enough hueing toeliminate the yellowing of dingy fabric.

TABLE 5 Multi-Wash Data for Cotton at 1 ppm of Hueing Agent in WashWater ΔE* after ΔE* after ΔE* after ΔE* after Hueing Agent 1 wash 3washes 5 washes 8 washes Inventive 1.2 2.1 2.2 2.2 Hueing Agent 1 (100%)Hueing Agent 2 (100%) 1.6 2.9 3.2 3.4

It should be noted that, unlike many traditional dyes, the polymericthiophene hueing agents of the present invention and laundry carecompositions containing the same do not require the inclusion of ableaching agent to remove the excess due to over-hueing of the fabric.The inventive hueing agents and compositions naturally build and leveloff on the fabric at desired amounts to impart a desired whiteningeffect to the consumer, without creating a dyed (e.g. over-hued) fabric.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the subject matter of this application (especiallyin the context of the following claims) are to be construed to coverboth the singular and the plural, unless otherwise indicated herein orclearly contradicted by context. The terms “comprising,” “having,”“including,” and “containing” are to be construed as open-ended terms(i.e., meaning “including, but not limited to,”) unless otherwise noted.Recitation of ranges of values herein are merely intended to serve as ashorthand method of referring individually to each separate valuefalling within the range, unless otherwise indicated herein, and eachseparate value is incorporated into the specification as if it wereindividually recited herein. All methods described herein can beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g., “such as”) provided herein, isintended merely to better illuminate the subject matter of theapplication and does not pose a limitation on the scope of the subjectmatter unless otherwise claimed. No language in the specification shouldbe construed as indicating any non-claimed element as essential to thepractice of the subject matter described herein.

Preferred embodiments of the subject matter of this application aredescribed herein, including the best mode known to the inventors forcarrying out the claimed subject matter. Variations of those preferredembodiments may become apparent to those of ordinary skill in the artupon reading the foregoing description. The inventors expect skilledartisans to employ such variations as appropriate, and the inventorsintend for the subject matter described herein to be practiced otherwisethan as specifically described herein. Accordingly, this disclosureincludes all modifications and equivalents of the subject matter recitedin the claims appended hereto as permitted by applicable law. Moreover,any combination of the above-described elements in all possiblevariations thereof is encompassed by the present disclosure unlessotherwise indicated herein or otherwise clearly contradicted by context.

We claim:
 1. A method for making an amide-containing, polymericthiophene hueing agent, wherein the amide is formed via hydrolysis of anitrile under basic conditions.
 2. The method of claim 1, wherein thebasic conditions are formed in the presence of at least one ofcarbonates, bicarbonates, amines, hydroxides, alkoxides, and mixturesthereof.